CN102408615A - Polyethylene geomembrane resin composition and preparation method thereof - Google Patents
Polyethylene geomembrane resin composition and preparation method thereof Download PDFInfo
- Publication number
- CN102408615A CN102408615A CN2010102895732A CN201010289573A CN102408615A CN 102408615 A CN102408615 A CN 102408615A CN 2010102895732 A CN2010102895732 A CN 2010102895732A CN 201010289573 A CN201010289573 A CN 201010289573A CN 102408615 A CN102408615 A CN 102408615A
- Authority
- CN
- China
- Prior art keywords
- lldpe
- resin combination
- geomembrane
- preparation
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/9298—Start-up, shut-down or parameter setting phase; Emergency shut-down; Material change; Test or laboratory equipment or studies
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polyethylene geomembrane resin composition. Taking the weight of linear low density polyethylene (LLDPE) as 100%, the resin composition comprises: LLDPE fusant, wherein the flow rate of the fusant is 0.5-10 g/10min; (2) 0.17%-0.51% of a complex cross-linking additive composed of 1,1-dimethylethyl-hydrogen peroxide and peroxide tert-butyl benzoate; (3) 0.017%-0.032% of benzoyl peroxide (BPO); and (4) 11%-35% of LLDPE-g-PS graft copolymer. With the adoption of the composition, the gradually enlarging of an LLDPE microcrosslinking structure is realized, the occurrence of gelling is avoided, and broad-width geomembrane with few fish eyes, high strength and good barrier property can be stably produced by blowing without any mixing, wherein the thickness of the geomembrane is thicker than or equal to 0.5 mm, and the breadth of the geomembrane is 5-8 mm. The application of the LLDPE in the fields, such as agriculture, water conservancy, transportation, environmental protection and port construction and the like is enlarged. The invention further discloses a preparation method of the resin composition.
Description
Technical field
The present invention relates to a kind of polyethylene resin composition; Be specifically related to the little cross-linking modified linear low density polyethylene of organo-peroxide (LLDPE) and add the second component LLDPE-g-PS graft copolymer, blow out wide cut geomembrane resin combination of intensity height, good barrier property and preparation method thereof.
Background technology
As everyone knows, geomembrane b referred to as " the 4th kind of building materials " after steel, cement, timber.After 20th century, introduced China the seventies, be widely used in the fields such as agricultural, water conservancy, traffic, environmental protection and port construction, played conserve water resource and antipollution effect.After getting into the eighties, flourish along with China's Vilaterm industry brings change in essence for the development of geomembrane.Because Vilaterm, excellent performance cheap, characteristics such as use easily, become the main body of geo-membrane material rapidly with it.Linear low density polyethylene (LLDPE) is the multipolymer of ethene and terminal olefin, and its molecule is linear structure, makes it have excellent tensile strength, tear strength, paracentesis resistance and relatively low price, is used by increasing geomembrane manufacturer.But the side chain of LLDPE is short; Short-chain branch distributes wide, causes its melt strength little, and it is low to extrude outlet viscosity; Melt drawdown property is big in blowfilm shaping processing; Bubble stability is poor, can't blow wide cut geotechnique canopy film separately because of the restriction of its processibility, makes the excellent rerum natura of LLDPE in geomembrane, to be able to give full play to.At present, domestic polyethylene film for earthwork mainly adopts the LDPE/LLDPE/HDPE blending resin to produce, and the bibliographical information of this respect is a lot, like document " three-layer co-extruded geomembrane production unit and technology " (rubber and plastic technology and equipment, 2003 29 6 phases of volume, 32～35 pages); " research of polyethylene film for earthwork weather resistance " (Chinese plastics; 2005 19 1 phases of volume; 53～58 pages) because the blending resin trade mark, performance and mixing proportion is different, cause the production difficulty big; Cost is high, and situation such as the geomembrane produced of blending is prone to that intensity is on the low side, barrier deviation, quality product are uneven.
After in a single day LLDPE realizes the independentization production of wide cut geomembrane, make it have characteristics such as barrier performance is good, intensity is high, ductility is good.In addition, in the application process of geomembrane, can also reduce weldering knot number of times, convenient construction reduces the laying expense, prevents that the seepage phenomenon from occurring, and is suitable for the abominable area of natural condition and uses.In the prior art, come the report of extrusion blow molding film a lot of about improving the LLDPE processibility.The cumyl superoxide that in LLDPE (MFR:2g/10min), adds 100～200ppm like USA4578431 carries out extrusion reaction, and the gained resin can be blow molded into the film of 25 μ m.(>=15g/10min) LLDPE carries out modification to clear 64-65146, and product is difficult for curling when the production casting films, is easy to processing to high melt flow rate(MFR) through adding linking agent.ZL03137608.8 adds ditertiary butyl peroxide in LLDPE (alpha olefin copolymer of C4～C8), be to carry out crosslinked extrused reaction under 0.3～0.6wt% at its consumption, makes a kind of canopy film resin compsn that is suitable for blowing 8000 * 0.08mm specification.React in the n-heptane solution of JP1113411 (A) proposition tert-butyl peroxide and LLDPE, obtain the good little crosslinked LLDPE of processibility.FR19840005549 adopts one or more superoxide and fused LLDPE reaction at least, prepares the resin that is suitable for extruding with blow molding.US4614764 (A) adopts a kind of LLDPE and another kind of through the LLDPE of organo-peroxide modification blend, and preparation is suitable for the resin combination of blown film.CN101538386A proposes ditertiary butyl peroxide DTBP and tertbutyl peroxide TBHP is composite forms, and compound proportion is 1: 1 to 6: 1, and its consumption is that 500～2500ppm carries out the thick canopy film of cross-linking modified blowing 80 μ m to LLDPE.
Above-mentioned patent documentation is limited at the melt strength that improves the LLDPE resin and the amplitude of improving aspect its blown film processing characteristics, can only blow ultrathin membrane and common wide cut canopy film.Because geomembrane thickness is big; Melt strength to resin requires high; Yet increasing substantially LLDPE resin melt intensity; Be unlikely again and cause film more " flake ", and do not see its relevant report through adding the resin dedicated Composition Aspects of wide cut geomembrane that the second component LLDPE graft copolymer prepares intensity height, good barrier property.
Summary of the invention
The object of the invention provides a kind of polyethylene film for earthwork resin combination and preparation method thereof.The increase rate of said composition melt strength is more than 2 times, and can produce intensity height, good barrier property wide cut geomembrane resin combination (thickness >=0.5mm, fabric width: 5～8m), wherein film surface " flake " is few.
Weight in linear low density polyethylene (LLDPE) is a hundred per cent, and polyethylene film for earthwork resin combination of the present invention comprises:
1)LLDPE 100％
2) composite crosslinking coagent 0.17%～0.51%
3) BPO (BPO) 0.017%～0.032%
4) LLDPE graft copolymer (LLDPE-g-PS) 11%～35%
Composite crosslinking coagent described in the compsn is 1,1-dimethyl ethyl-hydrogen peroxide (TB) and the composite composition of peroxidized t-butyl perbenzoate (TBPB), and the weight ratio of two kinds of crosslinking coagents is TB/TBPB=20: 1～4: 3.
Described LLDPE-g-PS is grafted to the graft copolymer on the LLDPE main chain with graftomer under action of evocating; Initiator was selected from the sad tert-butyl ester, t-butyl peroxy-acetate (TBPA), tertbutyl peroxide, 2; 5-dimethyl--2; A kind of in 5-di-t-butyl hexane peroxide, tert-butyl peroxide, Di Cumyl Peroxide 99, hydrogen phosphide cumene, peroxo-benzene first phthalein or the peroxide di-t-butyl preferably adopts Di Cumyl Peroxide 99 (DCP).Graftomer can be selected from a kind of in the multipolymer (HIPS) of cinnamic homopolymer (GPPS) or vinylbenzene and polybutadiene rubber, and (can be powdery or granular resin, melt flow rate(MFR) be 0.5～35g/10min to the homopolymer of optimization styrene.
The preparation method of described LLDPE-g-PS is: initiator and the acetone of getting 0.3～1.5 part are by weight being to be mixed with mixing solutions in 1: 2～1: 4; Then with 7～25 parts PS (PS) LLDPE mixed at high speed 3～5min with mixing solutions and 100 parts; Again mixed material is added in the twin screw extruder and carry out melting graft reaction, 170～220 ℃ of temperature of reaction, reaction times 5～12min; Extrude, cooling, granulation, obtain LLDPE-g-PS.
LLDPE described in the compsn adopts efficient ziegler-natta catalyst systems, is the copolymerization product of ethene and 1-butylene, MFR:0.5～10g/10min; Density: 0.916～0.927g/cm3; Mw:9～15 * 104; Mw/Mn:5～10; Catalyst residue amount Ti≤12ppm.Described melt flow rate(MFR) (MFR) is at 190 ℃, the measured value under the 2.16Kg load.
LLDPE described in the compsn can be powdery or granular resin, but best with powdered resin for reaching the better mixing effect.
Composite crosslinking coagent described in the compsn is the composite composition that TB and TBPB carry out different ratios.Wherein the scope of total add-on of composite crosslinking coagent is that the optimum mixture ratio of 0.17%～0.51%, two kinds of crosslinking coagents is TB/TBPB=9: 1～5: 3.Two kinds of superoxide are the commercially available prod, and its half life temperature is because of manufacturer's difference difference slightly, transformation period T=256～267 of general TB ℃/1min; Transformation period T=166～168 of TBPB ℃/1min.
BPO described in the compsn is the commercially available prod, and the half life temperature of superoxide is because of manufacturer's difference difference slightly, transformation period T=131～134 of general BPO ℃/1min, its amount ranges: 0.017%～0.032%.To the strict control of its used in amounts, consumption can not surpass 0.032%, and processing temperature can not be above 230 ℃ in the preparation of compositions process in addition; Reaction times can not be above 20 seconds; Otherwise degree of crosslinking is uncontrollable, is prone to gel, produces more " flake "; Make the wide cut geomembrane to process and to use, serious point can cause the screw rod locking to damage processing units.But its add-on can not be less than 0.017%, otherwise the increase rate of compsn melt strength is not enough, do not reach the requirement of blowing wide cut geomembrane.
The present invention also can add a certain amount of thermo-stabilizer and oxidation inhibitor in the preparation process of LLDPE-g-PS and polyethylene film for earthwork resin combination, its total add-on is 0.1%～0.5% (weight in LLDPE is per-cent).
The preparation of resin combination of the present invention also can be carried out in Banbury mixer, kneader, but is the best with the twin screw extruder.
Particularly; The preparation method of polyethylene film for earthwork resin combination provided by the invention comprises: earlier with adding solvent behind two kinds of crosslinking coagent proportional mixing; Add the LLDPE that accounts for total amount 5%～10% (wt) again, behind mixed at high speed 3～5min, process the premix masterbatch then; To remain LLDPE, premix masterbatch and LLDPE-g-PS then and joined together by charging opening and carry out extrusion reaction in the forcing machine, temperature of reaction is 165～220 ℃, and the reaction times is 1～3min; With BPO and solvent solution-forming, be added drop-wise in the forcing machine fluxing zone at last, control is no more than 20 seconds the residence time of BPO in forcing machine, and temperature of reaction is no more than 230 ℃, extrudes, cooling, granulation.
Resin combination of the present invention prepares in the process, in composite crosslinking coagent and BPO, adds solvent, and said solvent is a kind of in toluene, YLENE, the acetone, and its add-on is composite crosslinking coagent or BPO weight 2～4 times.
In the compsn of the present invention; At first select the composite cross-linking system of the superoxide composition of a kind of low activity and greater activity, make base resin carry out the precrosslink reaction earlier, can control the cross-linked speed and the crosslinking degree of resin effectively; Appropriateness improves the melt strength of resin; Avoiding a kind of superoxide of single use is not to occur excessively crosslinkedly, causes consumption excessive exactly, is unfavorable for problems such as safety, environmental protection, modification cost like this.Secondly; On basis with precrosslink structural resin, add a small amount of highly active organo-peroxide again, extrude under the strictness control in temperature of reaction and reaction times through reactivity; Little crosslinking reaction takes place once more; Make little crosslinking structure of compsn present " staged " controlled, amplification step by step, make the melt strength of base resin significantly improve, satisfy the high request of wide cut geomembrane the base resin melt strength; Simultaneously also avoid excessive, be prone to the problem of gel because of the melt strength increase rate of resin.In addition, certain crosslinked and grafting effect also takes place in the adding of the second component LLDPE-g-PS and crosslinking coagent, and this synergy makes that the phenyl ring among the LLDPE-g-PS is more remarkable to the reinforced effects of geotechnological film strength, barrier.This method can make said composition need not any blending just can stably blow out wide cut geomembrane (thickness >=0.5mm, fabric width: 5～8m), and product appearance do not have " flake " basically, satisfies the request for utilization of geomembrane.
Resin combination of the present invention makes little crosslinking structure of base resin LLDPE amplify step by step; Realized the controlled of degree of crosslinking; Prevent that gel from occurring; Melt strength can improve significantly, simultaneously along with the second component LLDPE-g-PS add can prepare a kind of " flake " less, the wide cut geomembrane polyethylene resin composition of high, the good barrier property of intensity.The preparation method of resin combination of the present invention has advantages such as flow process is short, technology is simple, cost of development is low, the construction cycle is short, the quality product fluctuation is little.
Embodiment
(1) raw material
1) resin
2) organo-peroxide
TB transformation period T=264 ℃/1min, the auxiliary reagent factory, Lanzhou
TBPB transformation period T=167 ℃/1min, the auxiliary reagent factory, Lanzhou
BPO transformation period T=133 ℃/1min, the auxiliary reagent factory, Lanzhou
TBPA transformation period T=159 ℃/1min, the auxiliary reagent factory, Lanzhou
DCP transformation period T=171 ℃/1min, skyization chemical plant, Shanghai
3) other auxiliary agent
Antioxidant 1010 Switzerland vapour Bagong department
Oxidation inhibitor B561 Switzerland vapour Bagong department
Calcium stearate Yangtse River in Chongqing chemical plant
Zinic stearas Yangtse River in Chongqing chemical plant
(2) performance test standard
Melt flow rate(MFR) MFR (g/10min) GB/T3682-2000
Density (g/cm
3) GB/T1033-1986
Film stretching intensity GB/T1040-1992
Film elongation at break GB/T1040-1992
Film tear strength GB/T16578
Water vapor permeation coefficient GB/T1037
(3) equipment and instrument
Φ 67 twin screw extruders are long/directly=34/1 German Lestreiz company
Plunger type metering pump range: 0～100 liter of/hour U.S. Paasche Fei De company
The fast mixing machine of 10 risings Fuxin plastics machinery factory
120 3 layers of compound inflation film manufacturing machine of Φ Dalian rubber and plastics machine factory
Embodiment and Comparative Examples
Enumerate following examples invention effect of the present invention is described, but protection scope of the present invention is not limited in these embodiment, each component is in the parts by weight of base resin LLDPE in the compsn.
Embodiment 1
(1) preparation of LLDPE-g-PS: the acetone of getting 0.8 part of DCP and 1.6 parts is put into beaker and is mixed; Again the solution that mixes and 100 parts of LLDPE (101AA), 15 parts of PS (666D) and 0.15 part of antioxidant 1010,0.15 part of calcium stearate are put into the 10L high-speed mixer together; Mixed at high speed 5min; The material that mixes is joined in Φ 67 twin screw extruders,, carry out melting graft reaction under the reaction times 9min condition 170～220 ℃ of temperature of reaction; Cooling, granulation obtain LLDPE-g-PS (percentage of grafting: 3.9%).
(2) preparation of polyethylene film for earthwork resin combination: with 0.43 part of TB and 0.03 part of TBPB with after 0.9 part of acetone solvent mixes; Add 5 parts of LLDPE (101AA) then, in the fast mixing machine of 10 risings, mix 3min, process the premix masterbatch; Taking out 15 parts of LLDPE-g-PS is joined in the forcing machine by charging opening with premix masterbatch and 95 parts of LLDPE (101AA) and 0.1 part of antioxidant 1010,0.1 part of calcium stearate; After barrel temperature is to react 2min under 165～200 ℃ of conditions, at last 0.017 part of BPO and 0.04 part of acetone solvent are mixed with solution, drip in the forcing machine fluxing zone; At barrel temperature is under 200～230 ℃; After the extrusion reaction 17 seconds, cooling, the polyethylene film for earthwork resin combination is prepared in granulation.Said composition is blown wide cut geomembrane (fabric width 8m, thickness 0.5mm) on 120 3 layers of compound blown film unit of Φ, composition properties and geomembrane performance are seen table 1, table 2 respectively.
Embodiment 2
(1) preparation of LLDPE-g-PS: the acetone of getting 1.1 parts of TBPA and 2.6 parts is put into beaker and is mixed; Again the solution that mixes and 100 parts of LLDPE (7042), 22 parts of PS (492J) and 0.1 part of antioxidant 1010,0.1 part of Zinic stearas are put into the 10L high-speed mixer together; Mixed at high speed 5min; The material that mixes is joined in Φ 67 twin screw extruders,, carry out melting graft reaction under the reaction times 9min condition 170～220 ℃ of temperature of reaction; Cooling, granulation obtain LLDPE-g-PS (percentage of grafting: 5.2%).
(2) preparation of polyethylene film for earthwork resin combination: with 0.41 part of TB and 0.05 part of TBPB with after 1.1 parts of xylene solvents mix; Add 7 parts of LLDPE (7042) then, in the fast mixing machine of 10 risings, mix 3min, process the premix masterbatch; Take out 19 parts of LLDPE-g-PS (percentage of grafting: 5.2%) join in the forcing machine by charging opening with premix masterbatch and 93 parts of LLDPE (7042) and 0.25 part of oxidation inhibitor B561,0.15 part of Zinic stearas; After barrel temperature is to react 2min under 165～200 ℃ of conditions, at last 0.019 part of BPO and 0.04 part of xylene solvent are mixed with solution, drip in the forcing machine fluxing zone; At barrel temperature is under 200～230 ℃; After the extrusion reaction 17 seconds, cooling, the polyethylene film for earthwork resin combination is prepared in granulation.Said composition is blown wide cut geomembrane (fabric width 8m, thickness 0.5mm) on 120 3 layers of compound blown film unit of Φ, composition properties and geomembrane performance are seen table 1, table 2 respectively.
Embodiment 3
(1) preparation of LLDPE-g-PS is fully identical with embodiment 1.
(2) preparation of polyethylene film for earthwork resin combination: with 0.38 part of TB and 0.07 part of TBPB with after 0.9 part of toluene solvant mixes; Add 5 parts of LLDPE (101AA) then, in the fast mixing machine of 10 risings, mix 3min, process the premix masterbatch; Take out 22 parts of LLDPE-g-PS (percentage of grafting: 3.9%) join in the forcing machine by charging opening with premix masterbatch and 95 parts of LLDPE (101AA) and 0.15 part of antioxidant 1010,0.05 part of calcium stearate; After barrel temperature is to react 2min under 165～200 ℃ of conditions, at last 0.021 part of BPO and 0.05 part of toluene solvant are mixed with solution, drip in the forcing machine fluxing zone; At barrel temperature is under 200～230 ℃; After the extrusion reaction 17 seconds, cooling, the polyethylene film for earthwork resin combination is prepared in granulation.Said composition is blown wide cut geomembrane (fabric width 8m, thickness 0.5mm) on 120 3 layers of compound blown film unit of Φ, composition properties and geomembrane performance are seen table 1, table 2 respectively.
Embodiment 4
(1) preparation of LLDPE-g-PS is fully identical with embodiment 1.
(2) preparation of polyethylene film for earthwork resin combination: with 0.27 part of TB and 0.07 part of TBPB with after 0.8 part of acetone solvent mixes; Add 7 parts of LLDPE (101AA) then, in the fast mixing machine of 10 risings, mix 3min, process the premix masterbatch; Take out 25 parts of LLDPE-g-PS (percentage of grafting: 3.9%) join in the forcing machine by charging opening with premix masterbatch and 93 parts of LLDPE (101AA) and 0.1 part of antioxidant 1010,0.1 part of calcium stearate; After barrel temperature is to react 2min under 165～200 ℃ of conditions, at last 0.024 part of BPO and 0.05 part of acetone solvent are mixed with solution, drip in the forcing machine fluxing zone; At barrel temperature is under 200～230 ℃; After the extrusion reaction 17 seconds, cooling, the polyethylene film for earthwork resin combination is prepared in granulation.Said composition is blown wide cut geomembrane (fabric width 8m, thickness 0.5mm) on 120 3 layers of compound blown film unit of Φ, composition properties and geomembrane performance are seen table 1, table 2 respectively.
Embodiment 5
(1) preparation of LLDPE-g-PS is fully identical with embodiment 1.
(2) preparation of polyethylene film for earthwork resin combination: with 0.24 part of TB and 0.08 part of TBPB with after 0.8 part of acetone solvent mixes; Add 7 parts of LLDPE (101AA) then, in the fast mixing machine of 10 risings, mix 3min, process the premix masterbatch; Take out 28 parts of LLDPE-g-PS (percentage of grafting: 3.9%) join in the forcing machine by charging opening with premix masterbatch and 93 parts of LLDPE (101AA) and 0.15 part of antioxidant 1010,0.05 part of calcium stearate; After barrel temperature is to react 2min under 165～200 ℃ of conditions, at last 0.027 part of BPO and 0.07 part of acetone solvent are mixed with solution, drip in the forcing machine fluxing zone; At barrel temperature is under 200～230 ℃; After the extrusion reaction 17 seconds, cooling, the polyethylene film for earthwork resin combination is prepared in granulation.Said composition is blown wide cut geomembrane (fabric width 8m, thickness 0.5mm) on 120 3 layers of compound blown film unit of Φ, composition properties and geomembrane performance are seen table 1, table 2 respectively.
Embodiment 6
(1) preparation of LLDPE-g-PS is fully identical with embodiment 1.
(2) preparation of polyethylene film for earthwork resin combination: with 0.21 part of TB and 0.09 part of TBPB with after 0.6 part of acetone solvent mixes; Add 7 parts of LLDPE (7042) then, in the fast mixing machine of 10 risings, mix 3min, process the premix masterbatch; Take out 30 parts of LLDPE-g-PS (percentage of grafting: 3.9%) join in the forcing machine by charging opening with premix masterbatch and 93 parts of LLDPE (7042) and 0.15 part of antioxidant 1010,0.05 part of calcium stearate; After barrel temperature is to react 2min under 165～200 ℃ of conditions, at last 0.029 part of BPO and 0.07 part of acetone solvent are mixed with solution, drip in the forcing machine fluxing zone; At barrel temperature is under 200～230 ℃; After the extrusion reaction 17 seconds, cooling, the polyethylene film for earthwork resin combination is prepared in granulation.Said composition is blown wide cut geomembrane (fabric width 8m, thickness 0.5mm) on 120 3 layers of compound blown film unit of Φ, composition properties and geomembrane performance are seen table 1, table 2 respectively.
Embodiment 7
(1) preparation of LLDPE-g-PS graft copolymer is fully identical with embodiment 2.
(2) preparation of polyethylene film for earthwork resin combination: with 0.40 part of TB and 0.11 part of TBPB with after 1.1 parts of xylene solvents mix; Add 7 parts of LLDPE (7042) then, in the fast mixing machine of 10 risings, mix 3min, process the premix masterbatch; Take out 33 parts of LLDPE-g-PS (percentage of grafting: 5.2%) join in the forcing machine by charging opening with premix masterbatch and 93 parts of LLDPE (7042) and 0.15 part of oxidation inhibitor B561,0.05 part of Zinic stearas; After barrel temperature is to react 2min under 165～200 ℃ of conditions, at last 0.031 part of BPO and 0.07 part of xylene solvent are mixed with solution, drip in the forcing machine fluxing zone; At barrel temperature is under 200～230 ℃; After the extrusion reaction 17 seconds, cooling, the polyethylene film for earthwork resin combination is prepared in granulation.Said composition is blown wide cut geomembrane (fabric width 8m, thickness 0.5mm) on 120 3 layers of compound blown film unit of Φ, composition properties and geomembrane performance are seen table 1, table 2 respectively.
Comparative Examples 1
(1) preparation of LLDPE-g-PS is fully identical with embodiment 1.
(2) preparation of polyethylene film for earthwork resin combination: other condition is identical with embodiment 1, and difference is not add in the preparation of compositions process TBPB, with 0.46 part of TB with after 0.9 part of acetone solvent mixes; Add 5 parts of LLDPE (101AA) then, in the fast mixing machine of 10 risings, mix 3min, process the premix masterbatch; Take out 15 parts of LLDPE-g-PS (percentage of grafting: 3.9%) join in the forcing machine by charging opening with premix masterbatch and 95 parts of LLDPE (101AA) and 0.1 part of antioxidant 1010,0.1 part of calcium stearate; After barrel temperature is to react 2min under 165～200 ℃ of conditions, at last 0.017 part of BPO and 0.04 part of acetone solvent are mixed with solution, drip in the forcing machine fluxing zone; At barrel temperature is under 200～230 ℃; After the extrusion reaction 17 seconds, cooling, the polyethylene film for earthwork resin combination is prepared in granulation.Said composition is blown wide cut geomembrane (fabric width gm, thickness 0.5mm) on 120 3 layers of compound blown film unit of Φ, composition properties and geomembrane performance are seen table 1, table 2 respectively.
Comparative Examples 2
(1) preparation of LLDPE-g-PS is fully identical with embodiment 2.
(2) preparation of polyethylene film for earthwork resin combination: other condition is identical with embodiment 2; Difference is in the preparation of compositions process BPO and TB and TBPB to be added simultaneously; That is: with 0.41 part of TB and 0.05 part of TBPB, 0.019 part of BPO and after 1.1 parts of xylene solvents mix; Add 7 parts of LLDPE (7042) then, in the fast mixing machine of 10 risings, mix 3min, process the premix masterbatch; Take out 19 parts of LLDPE-g-PS (percentage of grafting: 5.2%) join in the forcing machine by charging opening with premix masterbatch and 93 parts of LLDPE (7042) and 0.25 part of oxidation inhibitor B561,0.15 part of Zinic stearas; After barrel temperature is to react 2min under 165～200 ℃ of conditions, cooling, the polyethylene film for earthwork resin combination is prepared in granulation.Said composition is blown wide cut geomembrane (fabric width 8m, thickness 0.5mm) on 120 3 layers of compound blown film unit of Φ, composition properties and geomembrane performance are seen table 1, table 2 respectively.
Comparative Examples 3
(1) preparation of LLDPE-g-PS is fully identical with embodiment 1.
(2) preparation of polyethylene film for earthwork resin combination: other condition is identical with embodiment 3; Difference is not add in the preparation of compositions process BPO; That is: with 0.38 part of TB and 0.07 part of TBPB with after 0.9 part of toluene solvant mixes; Add 5 parts of LLDPE (101AA) then, in the fast mixing machine of 10 risings, mix 3min, process the premix masterbatch; Take out 22 parts of LLDPE-g-PS (percentage of grafting: 3.9%) join in the forcing machine by charging opening with premix masterbatch and 95 parts of LLDPE (101AA) and 0.15 part of antioxidant 1010,0.05 part of calcium stearate; After barrel temperature is to react 2min under 165～200 ℃ of conditions, cooling, the polyethylene film for earthwork resin combination is prepared in granulation.Said composition is blown wide cut geomembrane (fabric width 8m, thickness 0.5mm) on 120 3 layers of compound blown film unit of Φ, composition properties and geomembrane performance are seen table 1, table 2 respectively.
Comparative Examples 4
(1) preparation of LLDPE-g-PS is fully identical with embodiment 1.
(2) preparation of polyethylene film for earthwork resin combination: other condition is identical with embodiment 4; Difference is that the add-on of BPO in the preparation of compositions process is 0.034 part, that is: with 0.27 part of TB and 0.07 part of TBPB with after 0.8 part of acetone solvent mixes, add 7 parts of LLDPE (101AA) then; In the fast mixing machine of 10 risings, mix 3min; Process the premix masterbatch, (percentage of grafting: 3.9%) being joined in the forcing machine by charging opening with premix masterbatch and 93 parts of LLDPE (101AA) and 0.1 part of antioxidant 1010,0.1 part of calcium stearate, is under 165～200 ℃ of conditions behind the reaction 2min at barrel temperature to take out 25 parts of LLDPE-g-PS; At last 0.034 part of BPO and 0.08 part of acetone solvent are mixed with solution; Dripping in the forcing machine fluxing zone, is under 200～230 ℃ at barrel temperature, and extrusion reaction is after 17 seconds; Cooling, the polyethylene film for earthwork resin combination is prepared in granulation.Said composition is blown wide cut geomembrane (fabric width 8m, thickness 0.5mm) on 120 3 layers of compound blown film unit of Φ, composition properties and geomembrane performance are seen table 1, table 2 respectively.
Comparative Examples 5
The preparation of polyethylene film for earthwork resin combination: other preparation processes are fully identical with embodiment 5, and difference is that resin combination prepares and does not add LLDPE-g-PS in the process that composition properties and geomembrane performance are seen table 1, table 2 respectively.
Comparative Examples 6
(1) preparation of LLDPE-g-PS is fully identical with embodiment 1.
(2) preparation of polyethylene film for earthwork resin combination: other preparation processes are fully identical with embodiment 6; Difference is that the add-on that resin combination prepares LLDPE-g-PS in the process is 5 parts, that is: with 0.21 part of TB and 0.09 part of TBPB with after 0.6 part of acetone solvent mixes, add 7 parts of LLDPE (7042) then; In the fast mixing machine of 10 risings, mix 3min; Process the premix masterbatch, (percentage of grafting: 3.9%) being joined in the forcing machine by charging opening with premix masterbatch and 93 parts of LLDPE (7042) and 0.15 part of antioxidant 1010,0.05 part of calcium stearate, is under 165～200 ℃ of conditions behind the reaction 2min at barrel temperature to take out 5 parts of LLDPE-g-PS; At last 0.029 part of BPO and 0.07 part of acetone solvent are mixed with solution; Dripping in the forcing machine fluxing zone, is under 200～230 ℃ at barrel temperature, and extrusion reaction is after 17 seconds; Cooling, the polyethylene film for earthwork resin combination is prepared in granulation.Said composition is blown wide cut geomembrane (fabric width 8m, thickness 0.5mm) on 120 3 layers of compound blown film unit of Φ, composition properties and geomembrane performance are seen table 1, table 2 respectively.
Comparative Examples 7
(1) preparation of LLDPE-g-PS is fully identical with embodiment 2.
(2) preparation of polyethylene film for earthwork resin combination: other condition is identical with embodiment 7; Difference is in the preparation of compositions process to add that the extrusion reaction time is 27 seconds behind the BPO, that is: with 0.40 part of TB and 0.11 part of TBPB with after 1.1 parts of xylene solvents mix, add 7 parts of LLDPE (7042) then; In the fast mixing machine of 10 risings, mix 3min; Process the premix masterbatch, (percentage of grafting: 5.2%) being joined in the forcing machine by charging opening with premix masterbatch and 93 parts of LLDPE (7042) and 0.15 part of oxidation inhibitor B561,0.05 part of Zinic stearas, is under 165～200 ℃ of conditions behind the reaction 2min at barrel temperature to take out 33 parts of LLDPE-g-PS; At last 0.031 part of BPO and 0.07 part of xylene solvent are mixed with solution; Dripping in the forcing machine fluxing zone, is under 200～230 ℃ at barrel temperature, and extrusion reaction is after 27 seconds; Cooling, the polyethylene film for earthwork resin combination is prepared in granulation.Said composition is blown wide cut geomembrane (fabric width 8m, thickness 0.5mm) on 120 3 layers of compound blown film unit of Φ, composition properties and geomembrane performance are seen table 1, table 2 respectively.
The physicals * of table 1 geomembrane resin combination
| Numbering | MFR(g/10min) | Density (g/cm 3) | Melt strength cN |
| Embodiment 1 | 0.27 | 0.925 | 6.6 |
| Embodiment 2 | 0.35 | 0.923 | 7.3 |
| Embodiment 3 | 0.21 | 0.927 | 6.9 |
| Embodiment 4 | 0.14 | 0.931 | 7.1 |
| Embodiment 5 | 0.13 | 0.930 | 7.4 |
| Embodiment 6 | 0.17 | 0.928 | 7.7 |
| Embodiment 7 | 0.15 | 0.929 | 7.9 |
| Comparative Examples 1 | 0.47 | 0.921 | 4.7 |
| Comparative Examples 2 | 0.18 | 0.922 | 1.9 |
| Comparative Examples 3 | 0.43 | 0.921 | 4.2 |
| Comparative Examples 4 | 0.11 | 0.923 | 1.7 |
| Comparative Examples 5 | 0.17 | 0.924 | 5.9 |
| Comparative Examples 6 | 0.21 | 0.923 | 6.1 |
| Comparative Examples 7 | 0.04 | 0.924 | 1.1 |
*LLDPE (101AA powder) melt strength is 2.7cN, and LLDPE (7042 pellet) melt strength is 3.4cN.
The physical and mechanical properties of table 2 geomembrane and outward appearance situation
Claims (10)
1. polyethylene film for earthwork resin combination is a hundred per cent in the weight of LLDPE, comprising:
1)LLDPE 100％
2) composite crosslinking coagent 0.17%～0.51%
3)BPO 0.017％～0.032％
4)LLDPE-g-PS 11％～35％
Described composite crosslinking coagent is 1, the composite composition of 1-dimethyl ethyl-hydrogen peroxide and peroxidized t-butyl perbenzoate, and the weight ratio of the two is=20: 1～4: 3; Described LLDPE-g-PS is grafted to the graft copolymer on the LLDPE main chain with graftomer under action of evocating, described graftomer is selected from a kind of in the multipolymer of cinnamic homopolymer or vinylbenzene and polybutadiene rubber.
2. resin combination according to claim 1 is characterized in that the mixed weight ratio of two kinds of crosslinking coagents is 9: 1～5: 3.
3. resin combination according to claim 1 is characterized in that described graftomer is cinnamic homopolymer.
4. resin combination according to claim 1 is characterized in that described LLDPE is the multipolymer that adopts efficient ziegler-natta catalyst systems ethene and 1-butylene.
5. resin combination according to claim 1; The preparation method who it is characterized in that described LLDPE-g-PS is: initiator and the acetone of getting 0.3～1.5 part are by weight being to be mixed with mixing solutions in 1: 2～1: 4; Then with 7～25 parts PS LLDPE mixed at high speed 3～5min with mixing solutions and 100 parts; Again mixed material is added in the twin screw extruder and carry out melting graft reaction, 170～220 ℃ of temperature of reaction, reaction times 5～12min; Extrude, cooling, granulation, obtain LLDPE-g-PS.
6. resin combination according to claim 5; It is characterized in that described initiator was selected from the sad tert-butyl ester, t-butyl peroxy-acetate, tertbutyl peroxide, 2; 5-dimethyl--2, a kind of in 5-di-t-butyl hexane peroxide, tert-butyl peroxide, Di Cumyl Peroxide 99, hydrogen phosphide cumene, peroxo-benzene first phthalein or the peroxide di-t-butyl.
7. resin combination according to claim 5 is characterized in that described initiator is a Di Cumyl Peroxide 99.
8. resin combination according to claim 1; It is characterized in that in the preparation process of LLDPE-g-PS and described polyethylene film for earthwork resin combination, can adding thermo-stabilizer and oxidation inhibitor; Weight in LLDPE is per-cent, and its total add-on is 0.1%～0.5%.
9. the preparation method of a resin combination according to claim 1; It is characterized in that comprising: earlier with adding solvent behind two kinds of crosslinking coagent proportional mixing; Add the LLDPE that accounts for total amount 5%～10% (wt) again, behind mixed at high speed 3～5min, process the premix masterbatch then; To remain LLDPE, premix masterbatch and LLDPE-g-PS then and joined together by charging opening and carry out extrusion reaction in the forcing machine, temperature of reaction is 165～220 ℃, and the reaction times is 1～3min; With BPO and solvent solution-forming, be added drop-wise in the forcing machine fluxing zone at last, control is no more than 20 seconds the residence time of BPO in forcing machine, and temperature of reaction is no more than 230 ℃, extrudes, cooling, granulation.
10. preparation method according to claim 9; It is characterized in that preparing in the process at resin combination; In composite crosslinking coagent and BPO, add solvent, said solvent is a kind of in toluene, YLENE, the acetone, and its add-on is composite crosslinking coagent or BPO weight 2～4 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102895732A CN102408615B (en) | 2010-09-21 | 2010-09-21 | Polyethylene geomembrane resin composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102895732A CN102408615B (en) | 2010-09-21 | 2010-09-21 | Polyethylene geomembrane resin composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102408615A true CN102408615A (en) | 2012-04-11 |
| CN102408615B CN102408615B (en) | 2013-04-24 |
Family
ID=45910990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102895732A Active CN102408615B (en) | 2010-09-21 | 2010-09-21 | Polyethylene geomembrane resin composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102408615B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111038057A (en) * | 2019-12-31 | 2020-04-21 | 潍坊友容实业有限公司 | Multilayer composite geomembrane for saline-alkali soil remediation and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4578431A (en) * | 1983-08-31 | 1986-03-25 | Mobil Oil Corporation | Process for improving melt strength of ethylene polymers by treatment with organic peroxide |
| CN101525452A (en) * | 2009-03-03 | 2009-09-09 | 山东天鹤塑胶股份有限公司 | Metallocene geomembrane |
| CN101538386A (en) * | 2008-03-19 | 2009-09-23 | 中国石油天然气股份有限公司 | Agricultural polyethylene resin composition |
-
2010
- 2010-09-21 CN CN2010102895732A patent/CN102408615B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4578431A (en) * | 1983-08-31 | 1986-03-25 | Mobil Oil Corporation | Process for improving melt strength of ethylene polymers by treatment with organic peroxide |
| CN101538386A (en) * | 2008-03-19 | 2009-09-23 | 中国石油天然气股份有限公司 | Agricultural polyethylene resin composition |
| CN101525452A (en) * | 2009-03-03 | 2009-09-09 | 山东天鹤塑胶股份有限公司 | Metallocene geomembrane |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111038057A (en) * | 2019-12-31 | 2020-04-21 | 潍坊友容实业有限公司 | Multilayer composite geomembrane for saline-alkali soil remediation and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102408615B (en) | 2013-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106752633B (en) | A kind of easy spray coating polypropylene composite material and preparation method and application | |
| CN103540013A (en) | Nylon 6/polypropylene plastic alloy and preparation method thereof | |
| CN101704969A (en) | Wood plastic composite for injection and preparation method and application thereof | |
| CN101962453B (en) | Polyethylene greenhouse film resin composition and preparation method thereof | |
| CN102219959A (en) | Composite material for vehicle bumper and preparation method thereof | |
| CN104098833B (en) | One kind is used for heat-resisting master batch of polyacrylic antioxygen and preparation method thereof | |
| CN102352070A (en) | Cross-linking agent masterbatch used in dynamic sulfidation preparation of thermoplastic rubber and its prepared thermoplastic rubber | |
| CN102408615B (en) | Polyethylene geomembrane resin composition and preparation method thereof | |
| CN102408600B (en) | Metallocene polyethylene greenhouse film resin composition with high intensity and ultra-broad width, and its preparation method | |
| CN102295797B (en) | Zero-halogen flame-retardant polyolefin material and preparation method as well as application thereof | |
| CN101798400A (en) | Environmental-friendly degradable composite modified master batch and preparation method thereof | |
| CN102924797B (en) | Weathering resistance polyethylene agriculture film resin composition and preparation method thereof | |
| CN102408613B (en) | Polyethylene heavy packaging film resin composition and preparation method thereof | |
| CN102408601B (en) | Super-wide-breadth metallocene polyethylene greenhouse film resin composition and preparation method thereof | |
| CN103865176A (en) | Preparation method of high-melt-strength polypropylene | |
| CN102816369B (en) | Polyethylene resin combination for agricultural film and preparation method thereof | |
| CN102408614B (en) | Polyethylene greenhouse film resin composition with high intensity and ultra-broad width, and its preparation method | |
| CN102167855B (en) | Metallocene polyethylene greenhouse film resin composition | |
| CN103627070B (en) | Low-haze polyethylene film resin composition | |
| CN102286167B (en) | Toughened polypropylene resin composition and preparation method thereof | |
| CN103160015B (en) | Polyethylene resin composition for greenhouse film and preparation method thereof | |
| CN102924800B (en) | Polyethylene resin composition for weathering resistance agriculture film, and preparation method thereof | |
| CN102816364B (en) | Metallocene polyethylene resin composition for agricultural film and preparation method thereof | |
| CN102952319B (en) | Polyethylene agricultural film resin composition and its preparation method | |
| CN102408616B (en) | Over-wide polyethylene greenhouse film resin composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |